O nh-qo-



4 amino-anthraquinones. the benzoyl radical, for example, by a halogen atom,

3,060,180 ANTI-IRAQUINONE VAT DYESTUFFS CONTAIN- ING CHLORO-TRIAZENYL GROUPS Max Staeuble, Base], and Kurt Weber, Bottmingen, Switzerland, assignors to Ciba Limited, Basel, Switzerland N Drawing. Filed May 26, 1959, Ser. No. 815,785 Claims priority, application Switzerland May 30, 1958 6 Claims. ((31. 260-249) This invention provides valuable new anthraquinone vat dyestuffs which contain at least one aroylamino group and at least one group of the formula which is bound directly or through a bridge member to an aroyl residue, and in which X represents a hydrogen atom or a substituent. Advantageously, the new compounds correspond to the formula in which A represents an anthraquinone radical, m and n each represent the whole number 1 or 2, and X has the meaning given above.

The invention also provides a process for the manufacture of the above new dyestufis, wherein an aminoanthraquinone is reacted with a reactive derivative, more especially a chloride, of an aryl carboxylic acid which contains at least one group of the Formula 1 bound directly or through a bridge member to an aroyl radical, and, when the resulting reaction product contains a dichlorotriazine radical, if desired, exchanging one chlorine atom for a substituent containing at least two atoms.

As aminoanthraquinones suitable for the process of this invention there may be mentioned monoaminoand also diaminoanthraquinones, for example, l-aminoanthraquinone and simple substitution products thereof, such, for example, as 1-amino-4-methoxy-anthraquinone, 1- amino-4- or -5- or -8-acylaminoand especially -benzoy1- The latter may be substituted in methoxy, alkyl, trifluoromethyl, sulfonamido or alkylsulfone group. There may also be mentioned 1:5- and 1 S-diaminoanthraquinone and l :5-diamino-4 8-dioxyanthraquinone. There may also be mentioned those aminoanthraquinones which contain a further fused-on carbocyclic or heterocyclic ring, for example, 4-aminoanthraquinone-2: 1- (N) -acridone, 5 -amino-1 :9-isothiazoleanthrone, 4- or S-aminoanthrapyrimidine, mono-aminoor diamino-acedianthrones, 4- or 5-amino-1:1'-dianthrimide-carbazole, 4:4'- or 5:5'-diaInino-l:1-dianthrimidecarbazole, 4- or S-amino-S-benzoylamino-dianthrimidecarbazole or 4-amino-4'-benzoylamino-dianthrimide-carbazone, 4-amino-anthrapyridones, amino-dibenzanthrone, amino isodibenzanthrone, aminodibenzpyrenequinone, aminoanthrathrone, aminobenzanthrone, aminoflavanthrone, and also the compound of the formula I 0 som atent 3,060,18 Patented Oct. 23, 1962 EQQ As aryl-carboxylic acids there are advantageously used those of the formula A l tt cal, n and p each represent the whole number 1 or 2, and X represents a hydrogen atom or a substituent. As suitable substituents there may be mentioned chlorine atoms,

alkyl, phenyl, hydroxyl, alkoxy, hydroxyalkoxy, aryloxy, especially phenoxy, primary and secondary amino groups, for example, an NH group, a mono or di-alkylamino group, for example, monoor di-methylamino group, mono-or di-ethylamino group, a monobutyrylamino group, ethylene-imino group, monoor di-B-hydroxyethylamino group, monochloroethylamino or monocyanethylamino group, monoor di-carboxymethylamino group, or arylamino group, for example, an anthraquinonylamino group, and especially a phenylamino group, which may be substituted in the phenyl radical, advantageously by a hydrophilic group, for example, a carboxylic acid, sulfonic acid, sulfonamido, alkyl-sulfone or alkoxy group, and also groups capable of being converted into hydrophilic groups, for example, sulfofluoride, sulfochloride, carboxylic acid chloride, sulfonic acid ester or carboxylic acid ester groups. The symbol X may be an alkylmercapto or arylmercapto group, for example, a methylmercapto, carboxymethylmercapto, ethylmercapto or phenylmercapto group.

As examples of suitable aryl carboxylic acids of the Formula 3 there may be mentioned: 2-carboxyphenylamino-4:6 dichlorotriazines, 2 carboxypheny1amino-4- amino-6-chlorotriazines, 2-carboxyphenylamino-4-dimethylarnino-6-chlorotriazines, 2-carboxyphenylamino-4-ethylene-imino 6 chlorotriazines, 2:4 di (carboxyphenyl amino) -6-chlorotriazines, 2 carboxyphenyl-4:6-dichlorotriazines, 2:4-di-(carboxyphenyl)-6-chlorotriazines and 2 (3':5' dicarboxyphenylamino)-4-a1nino-6-chlorotriazine.

The reaction of the aminoanthraquinones with the re active derivatives, especially chlorides, of arylcarboxylic acids is advantageously carried out in an inert organic solvent, for example, nitrobenzene, chlorobenzene or ortho-dichlorobenzene, at a raised temperature. Arylmonocarboxylic acids of the Formula 3 are advantageously reacted in the molecular ratio 1:1 with the monoaminoanthraquinones or in the molecular ratio 2:1 with the diaminoanthraquinones. Aryldicarboxylic acids of the Formula 3 are advantageously reacted with monoaminoantharquinones in the ratio 1:2.

When there are used as starting materials those arylcarboxylic acids of the Formula 3, in which X represents a chlorine atom, that is to say compounds which contain a dichlorotriazine radical, a chlorine atom in the arylide so obtained may be exchanged for a substituent containing at least two atoms, for example, a hydroxyl, alkoxy, hydroxyalkoxy or aryloxy group or one of the primary or secondary amino groups or mercapto groups mentioned above.

The invention also includes a modification of the process described above, wherein an anthraquinone of the formula 3 is condensed with a compound of the formula Cl-(|J x N\ /N in which X has the meaning given above, and, when the reaction product so obtained contains two chlorine atoms in the triazine radical, one chlorine atom is exchanged for a substituent containing at least two atoms. Thus,

for example, one molecular proportion of the compound of the Formula 4 may be reacted with one molecular proportion of cyanuric chloride, and the resulting dichlorotriazine reacted, if desired, with a primary or secondary amine, or two molecular proportions of a compound of 4,. Example 1 3.9 parts of the triazine derivative of the formula l or the Formula 4 may be reacted with one molecular proportion of cyanuric chloride.

The dyestufi so obtained may be isolated from the medium in which they are produced and, notwithstanding the presence of an exchangeable halogen atom, they can be converted into useful dry dyestufi preparations; The dyestuff is advantageously isolated by filtration. The filtered dyestulf may be dried, if desired, after the addition of a neutral or weakly alkaline extender. Advantageously the drying is carried out at not too high a temperature, if desired, under reduced pressure.

The new dyestulfs are suitable for dyeing a very wide variety of materials, and especially for dyeing or printing textile materials of natural or regenerated cellulose by the usual vat dyeing or printing methods.

As the reactivity of the halogen atom in the triazine ring varies somewhat from compound to compound it is of advantage to adapt the method of dyeing, that is to say especially the concentration of the alkali or reducing agent, and the duration and temperature of the dyeing or steaming operation, to suit the dyestutf used. The most favourable conditions can easily be determined by preliminary tests.

In contradistinction to the conventional vat dyestufis, the dyestuffs of this invention are substantially irremovable from the fiber with hot dimethyl formamide so that it is probable that they are chemically bound on the fiber.

Dyeings produced with the dyestufis of this invention are fast to dry cleaning and migration. The dyed fabrics can therefore be coated with synthetic resins, for example, polyvinyl chloride, without the dyestutf migrating into the artificial resin. This is especially important in the manufacture of artificial leather.

The following examples illustrate the invention, the parts and percentages being by weight.

A iIH-oC-O is filtered off, washed with nitrobenzene and then with alcohol and dried in vacuo at 60 to C.

A dyestufif powder is thus obtained which is yellowish brown when dry; it dyes cotton and regenerated cellulose by the dyeing method described in Example 19 orangeyellow tints of very good fastness properties. The dyestuif is so securely fixed on the fiber that the strength of the dyeing is not substantially impaired even by a treatment with a hot organic solvent, such as dimethyl formamide or pyridine.

The 2:4 di (carboxyphenylamino) 6-chlorotriazine used as acylating component in this example can be prepared, for example, by condensing equimolecular proportions of the sodium salt of 4-aminobenzoic acid and cyanuric chloride in the molecular ratio of 2:1 in an aqueous medium at a temperature ranging from 0 to 40 C., by continuing the condensation at a slowly rising temperature until aminobenzoic acid can no longer be detected. To isolate the dicarboxylic acid derivative it is advantageous to adjust the pH value of the aqueous suspension with dilute hydrochloric acid to 2, filtering off the precipitate thus formed, washing it with water until free from acid and drying it in vacuo at 70 C.

Example 2 15.4 parts of 2:4-bis-(4'-carboxyphenylamino)-6-chloro-1:3:5-triazine are heated in 300 parts of nitrobenzene with 24 parts of thionyl chloride and 3 parts of dimethyl .formamide with stirring for 1 hour at 120 C. The excess thionyl chloride is distilled off in vacuo, at C. 20 parts of l-aminoanthraquinone are added, and the mixture is heated for 3 hours at C. The dyestutf of the formula 6 is isolated in the usual manner; it dyes cotton and regen- I Example 4 erated cellulose by the method described in Example 20 yellow tints having good fastnessproperties 3.9 parts of the triazine derivatlve of the formula The corresponding dyestutl from l-amino-4-benzoylaminoanthraquinone gives red dyeings of similar, good '5 properties. N I When in the above example the l-aminoanthraquinone l \C NH QOOOH is replaced by an equimolecular amount of 1-amino-6:7- II dichloroanthraquinone, an orange-yellow dyestufi of very good fastness properties is obtained. 0

Example 3 371 3.9 parts of the triazine derivative of the formula are suspended in 100 parts of trichlorobenzene and con- HOOC N 000E verted into the corresponding dicarboxylic acid chloride by being stirred at 100 to 105 C. with 4 parts of thionyl -f chloride. 6.9 parts of 1-amino-S-benzoylamino-anthra- N quinone and 0.1 part of dimethyl formamide are added, the temperature is raised to 160170 C. and the whole 6 is stirred on at this temperature for 3 hours. 1 After cooling, the dyestufi of the formula H Goo-1 111 0 (J1 0 NH--O o-O are suspended in 70 parts of dry nitrobenzene and con-- is filtered off, washed with trichlorobenzene and then with verted into the corresponding dicarboxylic acid chloride alcohol, and dried in vacuo at 7080 C. by being stirred at 110 C. with 4 partsof thionyl chlo- The dyestutf dyes cotton and regenerated cellulose by ride. The excess thionyl chloride is removed from the the method described in Example 19 yellow tints having solution in vacuo, and 6.9 parts of l-amino-S-benzoylvery good fastness properties. aminoanthraquinone are then added. The temperature The acylating component used in this example can be is raised to 160 C., 0.1 part of pyridine is added, and made, for example, in the following manner: the mixture is stirred on for 1 hour at 160 C. After Equirnolecular amounts of the sodium salt of 3-arnin0- cooling, the new dyestutl of the formula 4 benzoic acid and cyanuric chloride are condensed in the Q N C I IH-(3 o-rlrn N\ /N I II -ooNn b 61 o r m-00G is filtered off, washed with nitrobenzene and then with molecular ratio of 1:1 in an aqueous medium at 0-5 C. alcohol and dried in vacuo at 80 C. 60 On completion of the monocondensation, 1 molecular Cotton and regenerated cellulose are dyed by the proportion of 4-aminobenzoic acid is added in the form method described in Example 19 yellow tints having very of a neutral aqueous solution of the sodium salt and congood fastness properties. densation is performed at a temperature rising to 40 C. The acylating component used in this example can be until aminobenzoic acid can no longer be detected. To prepared, for example, by condensing equimolecular 65 isolate the asymmetrical dicarboxylic acid derivative the amounts of the sodium salt of 3-aminobenzoic acid and reaction mixture is acidified, and the product is filtered cyanuric chloride in the molecular ratio of 2:1 in an aqueofi, washed with water and dried in vacuo at 70 C. ous medium at a temperature ranging from 0 to C., by continuing the condensation at a slowly rising temperature until aminobenzoic acid can no longer be detected. 70 3.4 parts of 2-(4'-carboxyphenylamino)-4-amino-6- To isolate the dicarboxylic acid derivative the pH value chloro-1z3z5-triazine are suspended in parts of dry of the solution is advantageously adjusted to 2 with dilute nitrobenzene and 1.0 part of dirnethyl formamide, and hydrochloric acid, and the precipitate formed is filtered 3.0 parts of thionyl chloride are stirred The mixture off, washed until free from acid and dried in vacuo at is heated at 90-100 C. until a clear solution of the acid Example 5 to C. chloride is obtained. 3.4. parts of l-amino-S-benzoyl- 8 amino-anthraquinone are then added. The temperature is raised to 125 to 130 C., and the whole is stirred for a I 11 111 further'6 hours at this temperature, cooled to room temperature and the dyestutt of the formula N H o NH-O O-ONH-O CCl 1 C1 1'l g.

I 1 H NH: 0 0

l 2 H yellow. C -o o-NH o p 7 is filtered oflf, washed with methanol, and dried at 70 C. E I

The dyestufi produces on cotton and regenerated cellulose by the method described in Example 21 very fast orange-yellow prints.

The 2-(4'-carboxyphenylamino)-4 amino 6 chlorolz3z5-triazine used in this example can be prepared by I II condensation in an aqueous medium of a fine suspension Hm O of 2-amino-4z6-dichloro-l z3z5-triazine and the sodium 3 y salt of 4-aminobenzoic acid in the molecular ratio of 1:1 1 NHO at 3040 C., or by first condensing cyanuric chloride and the sodium salt of 4-aminobenzoic acid in an aqueous 25 medium at 0-4 C. to form 2-(4'-carboxyphenylamino)- 4:6-dich1oro-l 3:5-triazine and reacting a further chlorine atom at -40 C. with a slight excess of ammonia. g

Equally good results are obtained by using as the acylating component 2-(4-carboxylpheny1amino)-4-dimethyl- 3o 0 arnino-6-chloro-1z3z5-triazine of the formula N it iO HOOO@-NH( :o1 NN i Example 6 Farbogytghelylamlmo)A'dlethylammo'chlom 3.2 parts of 2-(4'-carboxyphenylamino)-4-amino-6- nazme o 6 0mm a 40 chloro-1:3:5-triazine are converted into the correspondp ing carboxylic acid chloride in 100 parts of nitrobenzene HOOC -NH-G CCl with 2.5 parts of thionyl chloride at 95100 C. The L 1; solution is treated with 0.2 part of pyridine and then with 1.4 parts of l:5-diarnino-4:S-dihydroxyanthraquinone, and the temperature is maintained at 120125 C. for 0 2 2 hours with stirring. The mixture is then heated for 1 These acylating components can be prepared in a manner hour at 150-l55 C., cooled to room temperature, and similar to that described in this example for the preparathe dyestufi of the formula tion of .2-(4'-carboxyphenylamino)-4-amino-6 chlorois filtered ofi and dried.

1:3:5-triazine, by condensing the sodium salt of 4-aminoa T yfl ye Cotton a d g a ed cel ulose benzoie acid in an aqueous medium with Z-dimethylamir O- blue-violet tints having very good fastness to solvents. 4:6-dich1orotriazine or with 2-diethylamino-4:6-dichloro- 1 Example 7 triazine respectively.

"Similar dyestufis which dye cotton and regenerated celiulose 'the tints shown in column III of the following 16.4 parts of 2-(4'-carboxyphenylamino)-4-amino-6- chloro-lz3z 5etriazine are converted into the corresponding carboxylic acid chloride in 100 parts of nitrobenzene table are obtained en in the above example qwith .5 parts of thionyl chloride in the presence of 0.5 5-b z y a q is replaced y an q part f pyridine at to C. The excess thionyl molecular amount of the starting materials listed in cOl- I chloride is expelled in vacuo and 2.4 parts of lzi-diaminoum 11 of'the following table: 75 anthraquinone are added to the solution. The tempera- 9 l ture is raised in the course of 1 hour to 150-155 C. and The acylating component used in this example can be the mixture is stirred for 3 hours at this temperature. prepared in an aqueous medium by condensing the so- The yellow-brown suspension of the dyestuff of the fordium salt of 4-aminobenzoic acid with cyanuric chloride mula at 0 to 5 C. in the molecular ratio of 1:1 and by furt r G -t ff 11TH: Ol(|] ICNH CONH 0 is isolated by filtration, washed with nitrobenzene and then ther adding one molecular proportion of the sodium with alcohol, and dried in vacuo at 70 C. salt of sulfanilic acid; this second condensation is per- The dyestuff dyes cotton and regenerated cellulose by formed at 30-40 C. by adding sodium hydroxide soluthe method described in Example 19 orange tints having tion dropwise at pH=6.0 to 7.5 until a solution is obgood fastness properties. The dyeing is fast even to hot tained and sulfanilic acid can no longer be detected.

organic solvents. The condensation product can be precipitated from its When in this example 2-(4'-carboxyphenylamino)-4'- solution in the form of the crystalline disodium salt by amino-6-chloro-l:3:5-triazine is replaced by an equithe addition of sodium chloride and then isolated by filmolecular amount of 2-(4-carboxyphenylamino)-4-ditration.

methylamino-6-chloro-l :3z5-triazine, or of 2-(4'-carboxy- Example 9 phenylamino)-4-diethylamino-6-chloro-1 :3 S-triazine, or

of 2- (3 -carboxyphenylamino -4-amino-6-chloro-l 3 5- triazine, dyestuflfs are obtained that have similar proper- 10.7 parts of 2:4-bis-(4carboxyphenyl)-6-hydroxy- 1:3:5-triazine are slowly heated with stirring to 110 C. in 100 parts of nitrobenzene with the addition of 24 parts of thionyl chloride and 2 parts of dimethyl formamide. Example 8 The resulting clear solution is maintained for 45 min- 5.1 parts of the condensaton product from 4-aminoutes at 110 C. and then cooled, whereupon the product benzoic acid, cyanuric chloride and sulfanilic acid of the crystallizes out in the form of long, fine needles. It is formula filtered oif, washed with dry petroleum ether and dried N in vacuo at room temperature. The product of the formula H 0 0 CC NH-(HJ (|3NH-S 03H 01 01 I ll ClOC- C C 00-01 are converted for use as an acylatmg component mto the corresponding carboxylic acid-sulfonic acid dichloride with 5.0 parts of thionyl chloride and 1.0 part of dicrystallizes from acetone in long, fine needles melting at methyl formamide by being heated for 2 hours at 212 C. (uncorrected). C. in 100 parts of nitrobenzene. 3.0 parts of 1- 4 parts of this acid chloride are made up at 60 C. amino-5-benzoylamino-anthraquinone are then added, into a clear solution in 150 parts of nitrobenzene. 6.9 and the whole is heated for 3 hours at to C. 50 parts of 1-amino-5-benzoylarnino-anthraquinone are then After cooling to room temperature, the orange-colored added, the whole is slowly heated to 120 C. and maindyestuff suspension is filtered 01f, washed with alcohol, tained at this temperature for 5 hours. The dyestufl of and dried in vacuo at 70-80 C. the formula l 05 t II The dyestulf of the probable formula is isolated in the usual manner; it dyes cotton and re- N NH-ooONn-o (|3NH- SO2C1 dyes cotton and regenerated cellulose yellow tints of very generated cellulose clear yellow tints of good fastness good fastness to washing. 75 properties. The corresponding dyestulf from l-aminoi2 anthraquinone yields a greenish yellow dyeing, and the is filtered off, washed with alcohol, and dried in vacuo at corresponding dyestufi from 1-amino-4-benzoylamino- 90 to Q anthraquinone produces red tints.

, The analogous dyestufiof the formula The dyestuff dyes cotton and regenerated cellulose by dyes cotton and regenerated cellulose from an alkaline the method described in Example 19 greenish blue tints hydrosulfite vat greenish blue tints of good fastness having good fastness properties. properties.

2:4-bis-(4'-carboxyphenyl)-6-hydroxy 1:3:5 triazine Exwiwle 12 can be prepared from 2:4-'bis-(4-tolyl)-6 h d -1;3;5- 4.2 parts of aminoacedrnanthrone are acylated with triazine by oxidation with potassium permanganate in an 3.2 Parts Of the CaPbOXYIiC 301d chloride of Y- lk aqumus Salution, phenylamino)-4-arnino-6-chloro 1:325 triazine in 100 parts of nitrobenzene and 0.2 part of pyridine by being Example 10 stirred for 6 hours at 140 to 150 C. After cooling to 9.4 parts of 2-(4'-car-boxyphenylamino)-4:6-'dichlororoom temperature, the dyestutf of the formula 1 3:5-triazine are heated in 350 'parts of nitrobenzene with O 12 parts of thionyl chloride and 1.5 parts of dimethyl 3 A formamide for 2 hours at 110 C. The excess thionyl chloride is distilled oif in vacuo, 10.2 parts of 4-aminoanthraquinone-Z:1(N)-acridone are added at 50 C., and

the whole is heated for 16 hours at 80 C. and for 6 hours 01 at 100 C. The resulting dyestufi of the formula 5 l N N I L smegma am. 0 NH 1 40 l N N O 4 is filtered off, washed with nitrobenzene and then with 5 alcohol, and dried in vacuo at 70 C.

The dyestufi dyes cotton and regenerated cellulose fast is isolated in the usual manner; it dyes cotton and regenbrown tints el'ated Cellulose greenish blue tints having g d 'P P Similar good results are obtained when in this example t 0f fastfless- 2-(4-carboxyphenylarnino)-4-arnino-6-chloro 113:5 tri- Example 11 azine is replaced by an equimolecular amount of 2-(4'- 88 parts of z (4, carboxyphenylamino) 4 amino clarbfoxyphlenylamino)-4-phenyl-6-chloro-1.3.5-tr1azine of chlor0-1:3:5-triazine are slowly heated in 350 parts of 6 0mm nitrobenzene with 12 parts of thionyl chloride and 1.5 parts of dimethyl formamide with stirring to 120 C., g whereupon the compound dissolves with evolution of hydrochloric acid. After 15 minutes the excess thionyl H chloride is distilled off in vacuo at 70 C., 10.2 parts of 4-aminoanthraquinone-2:1(N)-acridone are added, and N the mixture is heated for 2 hours at 100 C. and for 1 I hour at 120 C. After cooling, the blue dyestuff of the of YP Y -P Y- f l 3 :S-triazine of the formula I u NH CO HOOC-ONH-C oo N The aeylating components can be prepared in crystalline NH O0 form by condensing in an aqueous medium equimolecular H amounts of the sodium salt of 4-aminobenzoic acid and a finely dispersed suspension of 2-phenyl-4:6-dichlorotria- O V zine, or 2-phenoxy-4:6-dichlorotriazine respectively, at NHZ 40 C.

Example 13 3.2 parts of 2-(3-carboxyphenylamino) 4- amino-6- chloro-1:3:5-triazine are suspended in 100 parts of dry nitrobenzene and 2.0 parts of thionyl chloride are stirred in. The whole is heated to 90100 C., and in the course of 2 hours a clear solution of the corresponding carboxylic acid chloride is formed. 3.45 parts of 1- amino-S-benzoylamino-anthraquinone are then added and the temperature is raised to 135 to 140 C., the mixture is stirred on for 6 hours at this temperature and then cooled to room temperature. The dyestufi of the formula OCO-NH o 01 is filtered off, washed with alcohol, and dried in vacuo at 70 C.

The dyestuff dyes cotton and regenerated cellulose very fast orange-yellow tints.

The 2-(3-carboxyphenylamino)-4-amino 6 chloro- Go -1 u1 0 1:3:S-triazine used in this example can be prepared by condensing in an aqueous medium a fine suspension of 2- amino-4z6-dichloro-1:3:5-triazine and the sodium salt of 3-aminobenzoic acid in the molecular ratio of 1:1 at 30 to 40 C.

Example 14 6.1 parts of the carboxylic acid chloride of 2-(4'-carboxyphenylamino)-4:6-dichloro 1:3 :5 triazine are dissolved at 100 C. in 200 parts of nitrobenzene, 9.6 parts of l-aminoanthraquinone are added, the mixture is raised in the course of 45 minutes to 160 C. and stirred at this temperature for 5 hours.

The dyestufi of the formula dyes cotton and regenerated cellulose by the method described in Example 20 yellow tints of very good fastness properties.

The dyestuif of the formula I ll is prepared in an analogous manner and gives golden-' yellow dyeings from an alkaline hydrosulfite vat.

Example 15 7 parts of 2-(4'-carboxyphenyl)-4:6-dihydroxy-123:5-

triazine are heated in 250 parts of nitrobenzene, while being stirred, with 24 parts of thionyl chloride and 3 parts of dimethyl formamide to 105 C. and maintained at this temperature for 2 hours. The excess thionyl chloride is then distilled off in vacuo. At C., 13.7 parts of l-aminoanthraquinone are added, and the whole is raised to C. within 30 minutes, and then heated for 4 hours at 100 C., for 2 hours at C. and for 3 hours at C. The dyestutf of the formula I] ll 0 o is isolated in the usual manner; it dyes cotton and regenerated cellulose by the method described in Example 19 or 20 clear yellow tints having good fastness properties.

The dyestufi of the formula is prepared in an analogous manner; it dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat gold-orange tints of good fastness properties.

Equally fast, red dyeings are obtained with the analogous dyestufl from 1-amino-4-benzoylamino anthraquinone, While the dyestuif from 4-arninoanthraquinone- 2: 1 (N)-acridone yields greenish blue tints.

2- (4'-carboxyphenyl -4 6-dihydroxy-1 3 :S-triazine can be prepared from 2-(4-tolyl)-4:6-dihydroxy-1:3z5-triazine by oxidation with potassium permanganate in an alkaline aqueous solution.

Example 16 6.5 parts of 2-(4-carboxyphenylamino)-4-phenyl-6- chloro-1:3:5-triazine in 120 parts of nitrobenzene are heated in the presence of 4.8 parts of thionyl chloride for 1 hour at 110 C. The excess thionyl chloride is removed from the resulting clear solution by distillation under reduced pressure. At 80 C., 4.6 parts of l-aminoanthraquinone are added and the whole is maintained for 24 hours at 80 C. The dyestutf of the formula ii NH-COQ 15 16 is isolated in the usual manner; it dyes cotton and regen- The dyestufi dyes cotton and regenerated cellulose very erated cellulose by the method described in Example 19 fast blackish green tints. clear yellow tints of good fastness properties. When in this example aminoisodibenzanthrone is used The dyestufi of the formula instead of aminodibenzanthrone, a dyestuff results which N dyes cotton violet tints of similar properties. o NH-C 0C NH-o OO Exam 1e 18 i i.

2.3 parts of 4:5'-diamino-1:1'-dianthramide carbazole A are acylated with 3.2 parts of the carboxylic acid chloride 1 of 2-(4' carboxyphenylamino) 4 amino 6 chloro- 1 1:3:5-triazine as described in Example 7 and then isolated. 0 The dyestufi of the formula mN-( J J-HN-OOQ NH o N N I 31 II I l N o NH-O oONn-cl harm is obtained by using in the above example 7.6 parts of dyes cotton and regenerated cellulose brown tints having 2 (4' carboxyphenylamino) 4 phenoxy 6 chlorovery good properties of fastness. 1 :3:S-triazine; it gives similar, slightly more greenish When 2-(4'-carboxyphenylamino) 4 amino-6-chlorotints. 1:3:5-triazine is replaced by an equimolecular amount of Example 17 2 (4 carboxyphenylamino-4-phenylamino 6 chloro- 3.2 parts of 2-(4'-carboxypheny1arnino)-4-amino-6- 1:3 zs'tnazule of the formula chloro-l:3 :S-triazine are converted into the corresponding N carboxylic acid chloride in 100 parts of nitrobenzene with 4 parts of thionyl chloride with addition of 0.5 part of di- HOOC 1 (J-NEH methyl formamide at 100 to 110 C. The excess thionyl chloride is distilled oi the solution in vacuo, and 4.7 parts 0 l of aminodibenzanthrone are added. 0.5 part of pyridine I is then added and the whole is heated With stirring for 6 hours at 140 to 150 C., and then for 3 hours at 160 to 01' 0f yp enylamin0)-4-cyclohexylamino-6- 170 C. After cooling, the dyestufi of the formula r0-1I3I5-triaZ ne 0f the formula N N v 0 dyestuffs of similar properties are obtained. These acylating components can be prepared in an aqueous medium by condensing the sodium salt of 4- aminobenzoic acid with cyanuric chloride in the molecular ll l ratio of 121 at 0 to 5 C. and adding one molecular pro- NH O O /C NH2 portion of aniline hydrochloride or of cyclohexylamine N/ hydrochloride respectively; the second condensation is carried out at 3040 C. and a pH value of 6.5 to 7.5 by the dropwise addition of sodium hydroxide solution until a primary amino group can no longer be detected. The free carboxylic acid is then precipitated quantitatively with di- 0 lute hydrochloric acid and filtered off.

Example 19 14 parts of the dyestutf obtained as described in Example 1 are finely ground in a ball mill with 126 parts of a is filtered ofi, washed with nitrobenzene and then with neutral solution of 125 parts of dinaphthyl-methanealcohol, and dried in vacuo at 70 C. disulfonic acid in 1000 parts of water.

7.5 parts of the resulting paste are suspended in 250 parts of warm water. The dyestufi suspension thus obtained is added to a solution heated at 50 C. of 10 parts by volume of sodium hydroxide solution of 30% strength and 6 parts of sodium hydrosulfite in 1750 parts of water and vatted for 1 minute. 50 parts of cotton are dyed for 45 minutes in the dyebath prepared in this manner at 50 to 60 C. with addition of 60 parts of sodium chloride. After the dyeing the cotton is washed, oxidized, acidified, again thoroughly rinsed and soaped at the boil. An orange-yellow dyeing is obtained which has very good fastness properties.

Example 20 14 parts of the dyestufi obtained as described in Example 2 are finely ground in a ball mill with 126 parts of a neutral solution of 125 parts of dinaphthyl-methanedi sulfonic acid in 1000 parts of water. 10 parts of the resulting paste are suspended in 100 parts of water. A cotton fabric is impregnated with this suspension to a weight increase of 75% and then dried. The fabric is then impregnated with a solution containing per liter 16 grams of sodium hydroxide, 10 to 300 grams of sodium chloride and 30 grams of Rongalite (trade name for sodium sulfoxylate formaldehyde), squeezed to a weight increase of 75%, the dyeing is steamed for 1 to 9 minutes at 100 to 101 C., thoroughly rinsed in cold water, treated with a sodium bicarbonate solution of 0.5% strength,

rinsed, soaped for 20 minutes in a boiling 0.3% solution of a non-ionic detergent, rinsed and dried. A clear yellow dyeing of good fastness properties is obtained.

Example 21 28 parts of the dyestufi obtained as described in Example are ground in a ball mill with 112 parts of a neutral solution of 125 parts of dinaphthyl-methanedisulfonic acid in 1000 parts of water.

A printing paste is prepared from 100 parts of the dyestuff paste described above 300 parts of water 600 parts of thickening KB 1000 parts PREPARATION OF THICKENING KD (a) 20 parts of locust bean flour are strewn into 450 parts of water.

(b) 15 parts of wheat starch are pasted in 20 parts of water and diluted with 495 parts of boiling water.

(a) and (b) are combined, boiled for 20 minutes and 18 stirred until cold. 1 part by volume of aqueous formaldehyde solution of 30% strength is added as preservative.

The printing paste is printed on a fabric of cotton or staple fibers of regenerated cellulose on a roller printing machine. The fabric is dried, impregnated with a solution containing per liter 24 grams of sodium hydroxide, 70 grams of sodium hydrosul-fite, 50 grams of sodium sulfate and 20 grams of borax, squeezed to a weight increase of 70% and fixed for 24 seconds at C. in a Monforts reactor, thoroughly rinsed in cold water, oxidized at 40 C., in a solution containing per liter 5 parts by volume of hydrogen peroxide of 30% strength and 3 parts by volume of acetic acid of 40% strength, rinsed, soaped at the boil for 15 minutes, rinsed and dried.

A clear, yellow-orange print of excellent fastness properties results.

What is claimed is:

1. An anthraquinone vat dyestuif of the formula AHNOO N in which. A represents anthraquinonyl.

2. The dyestufi of the formula GONHA 3. The dyestuif of the formula I if I l NH-O o-O-rrn-o 5. The dyestufi of the formula T I i V N O NEE-COONH-] Hl-NH o H I E1 Goo-1 m o g I1TH-OO-C 6. The dyestufi of the formula References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Bergmann: The Chemistry of Acetylene and Related -Compounds, page 80, Interscience Publishers Inc., New

York (1948).

Hess et 21.: Nature, vol. 183, pages 260 to 261 (Jan. 24, 1959). 

1. AN ANTHRAQUINONE VAT DYESTUFF OF THE FORMULA 